Surface modification of silica in an aqueous environment

ABSTRACT

The present invention is drawn to a method of treating silica in an aqueous environment. The method can comprise steps of dispersing silica particulates in an aqueous environment to form an aqueous dispersion; reversing the net charge of a surface of the silica particulates from negative to positive using a surface activating agent, thereby forming surface-activated silica particulates dispersed in the water; and contacting the surface-activated silica particulates with organosilane reagents to form reagent-modified and surface-activated silica particulates.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.10/769,385, filed on Jan. 30, 2004 now U.S. Pat. No. 7,435,450, theentire disclosure of which is hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates generally to the modification of silica inan aqueous environment. More specifically, the present invention relatesto the preparation of reagent-modified and surface-activated silicaparticulates which can be used to prepare ink-jet media coatings.

BACKGROUND OF THE INVENTION

Ink-jet inks typically comprise an ink vehicle and a colorant, thelatter of which may be a dye or a pigment. Dye-based ink-jet inks usedin photographic image printing are almost always water-soluble dyes. Asa result, such dye-based ink-jet inks are usually not very water fast,i.e. images tend to shift in hue and edge sharpness is reduced uponexposure to humid conditions. In addition, images created from thesewater-soluble dye-based ink-jet inks tend to fade over time, such aswhen exposed to ambient light and/or air. Pigment-based inks on theother hand, allow the creation of images that are vastly improved inhumid fastness and image fade resistance. Pigment based images, however,are inferior to dye-based ink-jet inks with respect to the desirabletrait of color saturation.

Print media surfaces play a key role in the fade properties and humidfastness of ink-jet produced printed images. Thus, for a given ink, thedegree of fade and humid fastness can be dependent on the chemistry ofthe media surface. This is especially true in the case of dye-basedink-jet ink produced images. As a result, many ink-jet inks can be madeto perform better when an appropriate media surface is used.

In order for the ink-jet industry to effectively compete with silverhalide photography, it is desirable that ink-jet produced images becolor saturated, fade resistant, and humid fast, to name a few goals.Thus, enhanced permanence of dye-based ink-jet ink produced images isbecoming more and more integral to the long-term success ofphoto-quality ink-jet ink technologies.

A few categories of photographic ink-jet media are currently available,including polymer coated media, clay coated media, and porous coatedmedia. It is the polymer-coated media that provides for the longestlasting ink-jet ink produced images. However, this category of media isgenerally inferior in dry time and humid fastness relative to porouscoated media. On the other hand, image fade resistance and humidfastness of porous coated media is generally lower than that of itspolymer coated media counterpart. Therefore, there is a great desire toimprove the image permanence of ink-jet ink images printed on porouscoated media.

Image permanence improvements have been attempted via modification ofthe ink. They have also been attempted via modification of the media.Surface modification of porous media coatings is one of the methods ofmedia modification that has been attempted. Such modifications have beencarried out in organic solvents, which can be costly and complicated atscale up, as well as pose environmental concerns. Simpler and moreeconomical modification methods giving a desired end result would be anadvancement in the art.

SUMMARY OF THE INVENTION

In accordance with embodiments of the present invention, various methodscan be used to chemically modify porous inorganic particulates such thatthe modified particulates, when used as media coatings, provide certainadvantages related to image permanence. It has been discovered that suchmethods can be carried out in an aqueous environment, rather than intypical organic solvent-based environments.

In accordance with this, a method of treating silica in an aqueousenvironment can comprise dispersing silica particulates in an aqueousenvironment to form an aqueous dispersion; reversing the net charge of asurface of the silica particulates from negative to positive using asurface activating agent, thereby forming surface-activated silicaparticulates dispersed in the water; and contacting thesurface-activated silica particulates with organosilane reagents. Thismethod can result in reagent-modified and surface-activated silicaparticulates, also referred to herein as treated silica. In oneembodiment, these treated silica particulates can be used to prepareink-jet media sheets by the additional steps of preparing a porouscoating composition including the reagent-modified and surface-activatedsilica particulates and an organic binder, and coating the porouscoating composition on a media substrate.

In another embodiment, treated silica particulates for use in ink-jetmedia coatings can comprise silica particulates being surface-activatedby a member selected from the group consisting of an aluminum chloridehydrate, a trivalent metal oxide, a tetravalent metal oxide, andcombinations thereof. Further, the silica particulates can also bereagent-modified by an organosilane reagent. These treated silicaparticulates can be used to prepare ink-jet media sheets. Such a mediasheet can include a porous coating composition including the treatedsilica particulates and a binder admixed with the treated silicaparticulates. This porous coating composition can be coated on a mediasubstrate to form the ink-jet media sheet.

In another embodiment, a system for printing ink-jet images with minimaldye mobility can comprise a media sheet and an ink-jet ink. The mediasheet can have a porous coating composition coated thereon that includestreated silica particulates being reagent-modified and surface-activatedin an aqueous environment, wherein the treated silica particulates havea net positive charge. A binder can be admixed with the treated silicaparticulates to form the porous coating composition, and a mediasubstrate can have the porous coating composition coated thereon.Further, the ink-jet ink can have an anionic dye colorant configured forbeing printed on the media sheet.

Additional features and advantages of the invention will be apparentfrom the following detailed description which illustrates, by way ofexample, features of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Before particular embodiments of the present invention are disclosed anddescribed, it is to be understood that this invention is not limited tothe particular process and materials disclosed herein as such may varyto some degree. It is also to be understood that the terminology usedherein is used for the purpose of describing particular embodiments onlyand is not intended to be limiting, as the scope of the presentinvention will be defined only by the appended claims and equivalentsthereof.

In describing and claiming the present invention, the followingterminology will be used.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. Thus, for example, reference to“a dye” includes reference to one or more of such materials.

“Image permanence” refers to characteristics of an ink-jet printed imagethat relate to the ability of the image to last over a period of time.Characteristics of image permanence include image fade resistance, waterfastness, humid fastness, light fastness, smudge resistance, airpollution induced fading resistance, scratch and rub resistance, etc.

“Media substrate” or “substrate” includes any substrate that can becoated for use in the ink-jet printing arts including papers, overheadprojector plastics, coated papers, fabric, art papers, e.g., water colorpaper, and the like.

“Aluminum chloride hydrate,” “ACH,” “polyaluminum chloride,” “PAC,”“polyaluminum hydroxychloride,” or the like, refers to a class ofsoluble aluminum products in which aluminum chloride has been partlyreacted with base. The relative amount of OH compared to the amount ofAl can determine the basicity of a particular product. The chemistry ofACH is often expressed in the form Al_(n)(OH)_(m)Cl(_(3n-m)), wherein ncan be from 1 to 50, and m can be from 1 to 150. Basicity can be definedby the term m/(3n) in that equation. ACH can be prepared by reactinghydrated alumina Al(OH)₃ with hydrochloric acid (HCl). The exactcomposition depends upon the amount of hydrochloric acid used and thereaction conditions. Typically, the reaction can be carried out to givea product with a basicity of 40% to 60%, which can be defined as(%)=n/6×100. ACH can be supplied as a solution, but can also be suppliedas a solid.

There are other ways of referring to ACH, which are known in the art.Typically, ACH comprises many different molecular sizes andconfigurations in a single mixture. An exemplary stable ionic species inACH can have the formula [Al₁₂(OH)₂₄AlO₄(H₂O)₁₂]⁷⁺. Other examplesinclude [Al₆(OH)₁₅]³⁺, [Al₈(OH)₂₀]⁴⁺, [Al₁₃(OH)₃₄]⁵⁺, [Al₂₁(OH)₆₀]³⁺,etc. Other common names used to describe ACH or components that can bepresent in an ACH composition include Aluminum chloride hydroxide (8Cl);A 296; ACH 325; ACH 331; ACH 7-321; Aloxicoll; Aloxicoll LR; Aluminiumhydroxychloride; Aluminol ACH; Aluminum chlorhydrate; Aluminumchlorhydroxide; Aluminum chloride hydroxide oxide, basic; Aluminumchloride oxide; Aluminum chlorohydrate; Aluminum chlorohydrol; Aluminumchlorohydroxide; Aluminum hydroxide chloride; Aluminum hydroxychloride;Aluminum oxychloride; Aquarhone; Aquarhone 18; Astringen; Astringen 10;Banoltan White; Basic aluminum chloride; Basic aluminum chloride,hydrate; Berukotan AC-P; Cartafix LA; Cawood 5025; Chlorhydrol;Chlorhydrol Micro-Dry; Chlorhydrol Micro-Dry SUF; E 200; E 200(coagulant); Ekoflock 90; Ekoflock 91; GenPac 4370; Gilufloc 83;Hessidrex WT; HPB 5025; Hydral; Hydrofugal; Hyper Ion 1026; Hyperdrol;Kempac 10; Kempac 20; Kemwater PAX 14; Locron; Locron P; Locron S; Nalco8676; OCAL; Oulupac 180; PAC; PAC (salt); PAC 100W; PAC 250A; PAC 250AD;PAC 300M; PAC 70; Paho 2S; PALC; PAX; PAX 11S; PAX 16; PAX 18; PAX 19;PAX 60p; PAX-XL 1; PAX-XL 19; PAX-XL 60S; PAX-XL 61S; PAX-XL 69; PAX-XL9; Phacsize; Phosphonorm; (14) Poly(aluminum hydroxy) chloride;Polyaluminum chloride; Prodefloc AC 190; Prodefloc AL; Prodefloc SAB 18;Prodefloc SAB 18/5; Prodefloc SAB 19; Purachem WT; Reach 101; Reach 301;Reach 501; Sulzfloc JG; Sulzfloc JG 15; Sulzfloc JG 19; Sulzfloc JG 30;TAI-PAC; Taipac; Takibine; Takibine 3000; Tanwhite; TR 50; TR 50(inorganic compound); UPAX 20; Vikram PAC-AC 100S; WAC; WAC 2; Westchlor200; Wickenol 303; Wickenol CPS 325 Aluminum chlorohydrate Al₂ClH₅O₅ orAl₂(OH)₅Cl.2H₂O or [Al(OH)₂Cl]_(x) or Al₆(OH)₁₅Cl₃; Al₂(OH)₅Cl]_(x)Aluminum chlorohydroxide; Aluminum hydroxychloride; Aluminum chloride,basic; Aluminum chloride hydroxide; [Al₂(OH)_(n)Cl_(6-n)]_(m);[Al(OH)₃]_(n)AlCl₃; or Al_(n)(OH)_(m)Cl(_(3n-m)) (where generally,0<m<3n); for example. In one embodiment, preferred compositions includealuminum chlorides and aluminum nitrates of the formula Al(OH)₂X toAl₃(OH)₈X, where X is Cl or NO₃. In another embodiment, preferredcompositions can be prepared by contacting silica particles with analuminum chlorohydrate Al₂(OH)₅Cl or Al₂(OH)Cl₅.nH₂O. It is believedthat contacting a silica particle with an aluminum compound as describedabove causes the aluminum compound to become associated with or bind tothe surface of the silica particles. This can be either by covalentassociation or through an electrostatic interaction to form a cationiccharged silica, which can be measured by a Zeta potential instrument.

“Trivalent or tetravalent metal oxide” or “multivalent metal oxide”refers to compositions that can be used in conjunction with, or insteadof, ACH to reverse the charge of a silica surface from negative (−) topositive (+). Specifically, the negative charge on silica can bereversed by adsorbing an excess of positively charged polyvalent metaloxide on the surface. Coatings included oxides of trivalent andtetravalent metals such as aluminum, chromium, gallium, titanium, andzirconium. For example, acidified silica can be mixed with a basic metalsalt (such as Al₂O₃) to substantially cover the surface of silicaparticulates. By surface activation using such a multivalent metaloxide, the silica can carry a positive charge instead of negative chargeat below a pH of 7.

“Porous media coating” typically includes inorganic particulates, suchas silica particulates, bound together by a polymeric binder.Optionally, a mordant and/or other additives can also be present. Thecomposition can be used as a coating for various media substrates, andcan be applied by any of a number of methods known in the art. Inaccordance with the present invention, the inorganic particulates arereagent-modified and surface-activated.

“Active ligand” or “active moiety” includes any active portion of anorganosilane reagent that provides a function at or near the surface ofinorganic particles present in a porous media coating composition thatis not inherent to an unmodified inorganic porous particulate. Forexample, an active ligand can be used to reduce the need for binder in aporous media coating composition, or can be configured to interact witha dye or other ink-jet ink component, thereby improving permanence. Forexample, an amine can be present on an organosilane reagent to attractan anionic dye of an ink-jet ink.

“Organosilane reagent” or “reagent” includes compositions that comprisea desired moiety, such as an active ligand (or portion of the reagentthat provides desired modified properties to an inorganic particulatesurface of the porous media coating), which is covalently attached to asilane grouping. The organosilane reagent can become covalently attachedor otherwise attracted to the surface of silica particulates. Examplesof moieties that can provide a desirable function include anionic dyeanchoring groups (such as amines, quaternary ammonium salts, etc.),ultraviolet absorbers, metal chelators, hindered amine lightstabilizers, reducing agents, hydrophobic groups, ionic groups,buffering groups, or functionalities for subsequent reactions. Theactive moiety portion of the organosilane reagent can be directlyattached to the silane grouping, or can be appropriately spaced from thesilane grouping, such as by from 1 to 10 carbon atoms or other knownspacer groupings. The silane grouping of the organosilane reagent can beattached to inorganic particulates of the porous media coatingcomposition through hydroxyl groups, halo groups, or alkoxy groupspresent on the reagent. Alternatively, in some instances, theorganosilane reagent can be merely attracted to the surface of theinorganic particulates.

The term “lower” when referring to organic compounds or groups (when nototherwise specified) can contain from 1 to 8 carbons. For example, loweralkoxy can include methoxy, ethoxy, propoxy, butoxy, etc. Additionally,lower alkyl can include methyl, ethyl, propyl, isopropyl, butyl,t-butyl, hexyl, etc.

“Surface-activated” refers to the surface of silica after being treatedwith an inorganic surface activating agent, such as aluminum chloridehydrate and/or a multivalent metal oxide, in a sufficient amount tomodify the net charge of the surface from negative (−) to positive (+).This is not to say that all negatively charged moieties are converted topositive, but that the net charge of the entire surface is generallypositive.

“Reagent-modified” refers to silica modified by an organosilane reagent.Typically, the reagent can include an active ligand or moiety inaddition to the silane coupling group. It is not required that theorganosilane reagent be covalently attached to the surface of thesilica, though such attachment with respect to at least some of thereagent is believed to occur.

“Treated silica” refers to silica particulates that are bothsurface-activated with an inorganic surface modifying agent, as well asreagent-modified with an organosilane reagent.

The term “about” when referring to a numerical value or range isintended to encompass the values resulting from experimental error thatcan occur when taking measurements.

Ratios, concentrations, amounts, and other numerical data may bepresented herein in a range format. It is to be understood that suchrange format is used merely for convenience and brevity and should beinterpreted flexibly to include not only the numerical values explicitlyrecited as the limits of the range, but also to include all theindividual numerical values or sub-ranges encompassed within that rangeas if each numerical value and sub-range is explicitly recited. Forexample, a weight range of about 1 wt % to about 20 wt % should beinterpreted to include not only the explicitly recited concentrationlimits of 1 wt % to about 20 wt %, but also to include individualconcentrations such as 2 wt %, 3 wt %, 4 wt %, and sub-ranges such as 5wt % to 15 wt %, 10 wt % to 20 wt %, etc.

In accordance with the present invention, a method of treating silica inan aqueous environment can comprise steps of dispersing silicaparticulates in an aqueous environment to form an aqueous dispersion;reversing the net charge of a surface of the silica particulates fromnegative to positive using a surface activating agent, thereby formingsurface-activated silica particulates dispersed in the water; andcontacting the surface-activated silica particulates with organosilanereagents to form reagent-modified and surface-activated silicaparticulates.

Alternatively, a method of preparing an ink-jet media sheet can comprisethe steps of preparing a porous coating composition includingreagent-modified and surface-activated silica particulates and anorganic binder, and coating the porous coating composition on a mediasubstrate. The reagent-modified and surface-activated silicaparticulates can be prepared in accordance with the method of treatingsilica described above.

With either method, the preparation of the reagent-modified andsurface-activated silica particulates can be by a similar method. Forexample, in one embodiment, the aqueous dispersion described above caninclude the surface activating agent prior to the dispersing step, andthe reversing step can occur as the silica particulates are dispersed inthe aqueous dispersion portion-wise. In another embodiment, the surfaceactivating agent can be added to the aqueous dispersion after the silicaparticulates. In yet another embodiment, the dispersing step and thereversing step occur as both the silica particulates and the surfaceactivating agent are added to the aqueous environment simultaneously.The reagent can then be added to the silica after the reversing step, inone embodiment.

There are several advantages of the present invention. One of which isrelated to the ability to provide an active ligand or moiety as part ofa porous media coating wherein the active moiety is at or near thesurface of the inorganic particulates of a porous media coating. Inaddition, a silica surface with a net positive charge can be prepared toattract anionic components of an ink-jet ink. Thus, for example, apositive charge provided by an inorganic activating agent can attract ananionic dye to the silica surface, thereby reducing dye migration,bleed, and other issues often associated with dye-based ink-jet inkprinting. Additionally, because the active moiety of an organosilanereagent is also used, and is also at or near the surface of theparticulates of the porous media coating composition, a smaller amountof active ligand can be used to provide a desired result.

Other advantages include results achieved due to the presence of both anorganic and inorganic surface modifier. For example, organosilanereagent treated silica often provides poor coalescence, but can show airfade resistance gain. Conversely, silica treated with an inorganicsurface activating agent, such as aluminum chloride hydrate and/or amultivalent metal oxide, provides good coalescence performance, butpoorer air fade resistance. By incorporating both an organosilanereagent and an inorganic activating agent at or near the surface ofsilica, a balance between the good air fade resistance and goodcoalescence can be achieved. Additionally, by providing a system thatuses water as the preparative solvent, steps related to removing organicsolvent prior to media substrate coating can be eliminated.

The aqueous dispersion can include from 10 wt % to 40 wt % silicaparticulates with respect to the amount of water in the aqueousenvironment. As silica particulates tend to agglomerate or formaggregates in water, a high shear mixer, such as Ross mixer orrotor/stater mixer can be used to disperse the silica particulates to anaverage size from about 20 nm to about 500 nm. In one embodiment, thesilica can be sheared to form silica particulates or aggregates of anaverage size from about 50 nm to 300 nm.

With specific reference to the surface activating agent, in oneembodiment, the surface activating agent can be aluminum chloridehydrate. In another embodiment, the surface activating agent can be atrivalent or tetravalent metal oxide, with metals such as aluminum,chromium, gallium, titanium, and zirconium. If, for example, aluminumchloride hydrate is used, it can be present in the aqueous dispersion atfrom 2 wt % to 20 wt % compared to the silica content, and in a moredetailed embodiment, the aluminum chloride hydrate can be present atfrom 5 wt % to 10 wt %. Without being bound by any particular theory, itis believed that the aluminum of the aluminum chloride hydrateassociates with an oxygen at the surface of the silica particulates. Forexample, silica (SiO₂) typically includes Si—OH groups at the surface ofthe individual particulates, which can act as a weak acid, liberatinghydrogen and becoming ionized at a pH above about 2. As the pH israised, the surface of the silica becomes more negative. The addition ofaluminum chloride hydrate to silica causes the surface of the silica tobecome more positive. If enough aluminum chloride hydrate is added, thenthe net charge of the silica particulates becomes generally positive,which can be beneficial in the ink-jet arts when printing with anionicdye-containing ink-jet inks. It is believed that the aluminum of thealuminum chloride hydrate can interact with the ionized —Si—O⁻ group atthe surface of the silica, thus, converting some moieties at the surfaceto a more positive state. As stated, 2 wt % to 20 wt %, compared to thesilica content, is enough to achieve a desired degree of positive chargeat the silica surface. Thus, in this state, the silica is said to be“surface-activated.”

As the addition of aluminum chloride hydrate, trivalent metal oxide,and/or tetravalent metal oxide provides an inorganic means of addingpositive surface charge to silica, a more organic grouping can also beadded to provide increased positive charge, or provide another activeligand functionality. Specifically, organosilane reagents can be addedto the surface-activated silica to add additional positively chargedmoieties to the surface, or to provide another desired function at ornear the surface, e.g., ultraviolet absorber, chelating agent, hinderedamine light stabilizer, reducing agent, hydrophobic group, ionic group,buffering group, or functionality for a subsequent reaction. As thesereagents are primarily organic, they can provide different propertieswith respect to ink-jet ink receiving properties. For example, using acombination of aluminum chloride hydrate and an organosilane reagent canresult in improved water fastness, improved humid fastness, improvedcolor gamut, and reduced cracking.

In one embodiment, the organosilane reagents can be amine-containingsilanes. In a more detailed embodiment, the amine-containing silanes caninclude quaternary ammonium salts. Examples of amine-containing silanesinclude 3-aminopropyltrimethoxysilane,N-(2-aminoethyl-3-aminopropyltrimethoxysilane,3-(triethoxysilylpropyl)-diethylenetriamine,poly(ethyleneimine)trimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminoethylaminopropyl trimethoxysilane, andthe quaternary ammonium salts of the amine coupling agents mentionedabove. An example of a quaternary ammonium salt organosilane reagentincludes trimethoxysilylpropyl-N,N,N-trimethylammonium chloride.

Alternatively, other organosilane coupling agents can be useful for themodification of a silica surface, includingbis(2-hydroethyl)-3-aminopropyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,bis(triethoxysilylpropyl)disulfide, 3-aminopropyltriethoxysilane,3-aminopropylsilsesquioxane, bis-(trimethoxysilylpropyl)amine,N-phenyl-3-aminopropyltrimethoxysilane,N-aminoethyl-3-aminopropylmethyldimethoxysilane,3-ureidopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,N-(trimethyloxysilylpropyl)isothiouronium chloride,N-(triethoxysilpropyl)-O-polyethylene oxide,3-(triethoxylsilyl)propylsuccinic anhydride,3-(2-imidazolin-1-yl)propyltriethoxysilane, and reagents sold under thetrade name SILQUEST (OSI Products), SiventoSilane (Degussa), Dynasylan,and/or Cab-O-Sil M-5 (Cabot Corp.).

Other organosilane reagents can also be used that provide a benefit to aprinting system, such as reagents that include an active ligand ormoiety. Examples of such active ligands or moieties include those thatact as an ultraviolet absorber, chelating agent, hindered amine lightstabilizer, reducing agent, hydrophobic group, ionic group, bufferinggroup, or functionality for a subsequent reaction. To illustrate this,Formula 1 provides examples of organosilane reagents that canaccordingly be used:

In Formula 1 above, from 0 to 2 of the R groups can be H, —CH₃, —CH₂CH₃,or —CH₂CH₂CH₃; from 1 to 3 of the R groups can be halo or alkoxy; andfrom 1 to 3 of the R groups can be an active ligand or moiety, such asone described previously. If halo is present, then Formula 1 can be saidto be an organohalosilane reagent. If alkoxy is present, then Formula 1can be said to be an organoalkoxysilane reagent.

The active ligand or moiety can be any composition that can be part ofthe organosilane reagent of Formula 1, provided it is compatible withwater when integrated as part of the reagent. An inclusive list ofactive moieties in addition to that described previously can includestraight or branched alkyl having from 1 to 22 carbon atoms, cyano,amino, halogen substituted amino, carboxy, halogen substituted carboxy,sulfonate, halogen substituted sulfonate, halogen, epoxy, furfuryl,mercapto, hydroxyl, pyridyl, imidazoline derivative-substituted loweralkyl, lower cycloalkyl, lower alkyl derivatives of cycloalkyl, lowercycloalkenyl, lower alkyl derivatives of cycloalkenyl, lowerepoxycycloalkyl, lower alkyl derivatives of epoxycycloalkyl, phenyl,alkyl derivatized phenyl, phenoxy, poly(ethylene oxides), poly(propyleneoxide), copolymer of polyethyleneoxide and poly(propyleneoxide), vinyl,benzylic halogen, alkyl derivatized phenoxy, quaternary amine,monoethyleneimine, or polyethyleneimine.

There are many alternative methods of treating silica particulates withan inorganic surface activating agent and an organosilane reagent.Aluminum chloride hydrate will be described for exemplary purposes,though other surface activating agents could likewise be used.Specifically, an inorganic surface activating agent can be added towater prior to silica, and then the silica can be added portion-wiseover a period of time. Alternatively, the silica can be dispersed inwater first, and then the inorganic surface activating agent can beadded to the silica dispersion. In this embodiment, the ACH can be addedall at once, or portion-wise, depending on the desired result. Inanother embodiment, both the silica and the inorganic surface activatingagent can be added to water simultaneously. In each of theseembodiments, the net surface charge of the silica can be converted fromnegative (−) to positive (+). This does not mean that every negativelycharged moiety is necessarily converted from negative to positive, butthat the surface charge as a whole becomes more positive than negative.Typically, after combining the inorganic surface activating agent andthe silica, the organosilane reagent can then be added, though thisorder of addition is not required. For example, in one embodiment, afterforming the silica/inorganic surface activating agent composition asdescribed above, an organosilane reagent can be added to an inorganicsurface activating agent treated silica portion-wise. Such an additionscheme can prevent flocculation of the silica. In this embodiment, thepH can be controlled to maintain the colloidal stability of the silicadispersion. Alternatively, the ACH and the organosilane reagent can beadded simultaneously to a silica dispersion. In each of these reactionschemes, little or no organic solvent needs to be used. For example, theaqueous environment can include a predominant amount of water, and canoptionally include small amounts of organic solvent, surfactant,crosslinking agent such as boric acid, etc. Further, in someembodiments, it may be desirable to include mordants and/or otheradditives in the coating composition.

As mentioned, treated silica particulates for use in ink-jet mediacoatings can comprise silica particulates being surface-activated by amember selected from the group consisting of an aluminum chloridehydrate, a trivalent metal oxide, a tetravalent metal oxide, andcombinations thereof. The silica particulates can also bereagent-modified by an organosilane reagent. The treated silicaparticulates can be prepared in accordance with the preparative methodsdescribed previously. Additionally, a media sheet having a treatedsilica particulate-containing coating can comprise a porous coatingcomposition, including treated silica particulates beingsurface-treated, such as in an aqueous environment, with organosilanereagents and surface activating agent. The treated silica particulatescan be admixed with a binder to form a porous coating composition, and amedia substrate can have the porous coating composition coated thereon.The media substrate can be of any substrate known in the art, and caninclude papers, overhead projector plastics, coated papers, fabric, artpapers, e.g., water color paper, photobase, or the like. The applicationof the porous coating composition to a media substrate can be by anymethod known in the art, such as air knife coating, blade coating, gateroll coating, doctor blade coating, Meyer rod coating, roller coating,reverse roller coating, gravure coating, brush coating, or sprayercoating.

As the treated silica typically has a net positive charge due to thepresence of an inorganic surface activating agent, as well as anorganosilane reagent that can optionally be positively charged, ink-jetinks that include anionic components can be prepared that work well withthese media coatings. Specifically, if anionic dyes are present in anink-jet ink, then the dye can be subject to dye mobilization on atreated silica media coating, thereby providing good image permanencewith little dye migration.

This being stated, a system for printing ink-jet images with minimal dyemobility can comprise a media sheet and an ink-jet ink. The media sheetcan have a porous coating composition coated thereon that includestreated silica particulates being reagent-modified and surface-activatedin an aqueous environment, wherein the treated silica particulates havea net positive charge. A binder can be admixed with the treated silicaparticulates to form the porous coating composition, and a mediasubstrate can have the porous coating composition coated thereon.Further, the ink-jet ink can have an anionic dye colorant configured forbeing printed on the media sheet.

Though any effective amount of dye can be used in this system, theink-jet ink can include from 0.1 wt % to 10 wt % of the dye. Examples ofsuitable anionic dyes include a large number of water-soluble acid anddirect dyes. Specific examples of anionic dyes include the Pro-Jetseries of dyes available from Avecia Ltd., including Pro-Jet Yellow I(Direct Yellow 86), Pro-Jet Magenta I (Acid Red 249), Pro-Jet Cyan I(Direct Blue 199), Pro-Jet Black I (Direct Black 168), and Pro-JetYellow 1-G (Direct Yellow 132); Aminyl Brilliant Red F-B (SumitomoChemical Co.); the Duasyn line of “salt-free” dyes available fromHoechst, such as Duasyn Direct Black HEF-SF (Direct Black 168), DuasynBlack RL-SF (Reactive Black 31), Duasyn Direct Yellow 6G-SF VP216(Direct Yellow 157), Duasyn Brilliant Yellow GL-SF VP220 (ReactiveYellow 37), Duasyn Acid Yellow XX-SF VP413 (Acid Yellow 23), DuasynBrilliant Red F3B-SF VP218 (Reactive Red 180), Duasyn Rhodamine B-SFVP353 (Acid Red 52), Duasyn Direct Turquoise Blue FRL-SF VP368 (DirectBlue 199), and Duasyn Acid Blue AE-SF VP344 (Acid Blue 9); mixturesthereof; and the like. Further examples include Tricon Acid Red 52,Tricon Direct Red 227, and Tricon Acid Yellow 17 (Tricon ColorsIncorporated), Bernacid Red 2BMN, Pontamine Brilliant Bond Blue A, BASFX-34, Pontamine, Food Black 2, Catodirect Turquoise FBL Supra Conc.(Direct Blue 199, Carolina Color and Chemical), Special Fast Turquoise8GL Liquid (Direct Blue 86, Mobay Chemical), Intrabond Liquid TurquoiseGLL (Direct Blue 86, Crompton and Knowles), Cibracron Brilliant Red 38-A(Reactive Red 4, Aldrich Chemical), Drimarene Brilliant Red X-2B(Reactive Red 56, Pylam, Inc.), Levafix Brilliant Red E-4B (MobayChemical), Levafix Brilliant Red E-6BA (Mobay Chemical), Pylam CertifiedD&C Red #28 (Acid Red 92, Pylam), Direct Brill Pink B Ground Crude(Crompton & Knowles), Cartasol Yellow GTF Presscake (Sandoz, Inc.),Tartrazine Extra Conc. (FD&C Yellow #5, Acid Yellow 23, Sandoz, Inc.),Catodirect Yellow RL (Direct Yellow 86, Carolina Color and Chemical),Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.), D&C Yellow #10(Yellow 3, Tricon), Yellow Shade 16948 (Tricon), Basacid Black X34(BASF), Carta Black 2GT Sandoz, Inc.), Neozapon Red 492 (BASF), OrasolRed G (Ciba-Geigy), Direct Brilliant Pink B (Crompton-Knolls), AizenSpilon Red C-BH (Hodagaya Chemical Company), Kayanol Red 3BL (NipponKayaku Company), Levanol Brilliant Red 3BW (Mobay Chemical Company),Levaderm Lemon Yellow (Mobay Chemical Company), Aizen Spilon YellowC-GNH (Hodagaya Chemical Company), Spirit Fast Yellow 3G, Sirius SupraYellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz), Pergasol YellowCGP (Ciba-Geigy), Orasol Black RL (Ciba-Geigy), Orasol Black RLP(Ciba-Geigy), Savinyl Black RLS (Sandoz), Dermacarbon 2GT (Sandoz),Pyrazol Black BG (ICI Americas), Morfast Black Conc A (Morton-Thiokol),Diazol Black RN Quad (ICI Americas), Orasol Blue GN (Ciba-Geigy),Savinyl Blue GLS (Sandoz, Inc.), Luxol Blue MBSN (Morton-Thiokol),Sevron Blue 5GMF (ICI Americas), and Basacid Blue 750 (BASF); LevafixBrilliant Yellow E-GA, Levafix Yellow E2RA, Levafix Black EB, LevafixBlack E-2G, Levafix Black P-36A, Levafix Black PN-L, Levafix BrilliantRed E6BA, and Levafix Brilliant Blue EFFA, all available from Bayer;Procion Turquoise PA, Procion Turquoise HA, Procion Turquoise Ho5G,Procion Turquoise H-7G, Procion Red MX-5B, Procion Red H₈B (Reactive Red31), Procion Red MX 8B GNS, Procion Red G, Procion Yellow MX-8G, ProcionBlack H-EXL, Procion Black P-N, Procion Blue MX-R, Procion Blue MX-4GD,Procion Blue MX-G, and Procion Blue MX-2GN, all available from ICIAmericas; Cibacron Red F-B, Cibacron Black BG, Lanasol Black B, LanasolRed 5B, Lanasol Red B, and Lanasol Yellow 46, all available fromCiba-Geigy; Baslien Black P-BR, Baslien Yellow EG, Baslien BrilliantYellow P-3GN, Baslien Yellow M-6GD, Baslien Brilliant Red P-3B, BaslienScarlet E-2G, Baslien Red E-B, Baslien Red E-7B, Baslien Red M-5B,Baslien Blue E-R, Baslien Brilliant Blue P-3R, Baslien Black P-BR,Baslien Turquoise Blue P-GR, Baslien Turquoise M-2G, Baslien TurquoiseE-G, and Baslien Green E-6B, all available from BASF; Sumifix TurquoiseBlue G, Sumifix Turquoise Blue H-GF, Sumifix Black B, Sumifix BlackH-BG, Sumifix Yellow 2GC, Sumifix Supra Scarlet 2GF, and SumifixBrilliant Red 5BF, all available from Sumitomo Chemical Company;Intracron Yellow C-8G, Intracron Red C-8B, Intracron Turquoise Blue GE,Intracron Turquoise HA, and Intracron Black RL, all available fromCrompton and Knowles, Dyes and Chemicals Division; Pro-Jet 485 (a copperphthalocyanine); Magenta 377; mixtures thereof; and the like. This listis intended to be merely exemplary, and should not be consideredlimiting.

As mentioned, the ink-jet ink compositions of the present invention aretypically prepared in an aqueous formulation or liquid vehicle which caninclude water, cosolvents, surfactants, buffering agents, biocides,sequestering agents, viscosity modifiers, humectants, binders, and/orother known additives. Typically, the ink-jet ink compositions of thepresent invention have a viscosity of between about 0.8 to about 8 cps.In one aspect of the present invention, the liquid vehicle can comprisefrom about 70 wt % to about 99.9 wt % of the ink-jet ink composition. Inanother aspect, other than the colorant, liquid vehicle can also carrypolymeric binders, latex particulates, and/or other solids.

As described, cosolvents can be included in the ink-jet compositions ofthe present invention. Suitable cosolvents for use in the presentinvention include water soluble organic cosolvents, but are not limitedto, aliphatic alcohols, aromatic alcohols, diols, glycol ethers,poly(glycol) ethers, lactams, formamides, acetamides, long chainalcohols, ethylene glycol, propylene glycol, diethylene glycols,triethylene glycols, glycerine, dipropylene glycols, glycol butylethers, polyethylene glycols, polypropylene glycols, amides, ethers,carboxylic acids, esters, organosulfides, organosulfoxides, sulfones,alcohol derivatives, carbitol, butyl carbitol, cellosolve, etherderivatives, amino alcohols, and ketones. For example, cosolvents caninclude primary aliphatic alcohols of 30 carbons or less, primaryaromatic alcohols of 30 carbons or less, secondary aliphatic alcohols of30 carbons or less, secondary aromatic alcohols of 30 carbons or less,1,2-diols of 30 carbons or less, 1,3-diols of 30 carbons or less,1,5-diols of 30 carbons or less, ethylene glycol alkyl ethers, propyleneglycol alkyl ethers, poly(ethylene glycol) alkyl ethers, higher homologsof poly(ethylene glycol) alkyl ethers, poly(propylene glycol) alkylethers, higher homologs of poly(propylene glycol) alkyl ethers, lactams,substituted formamides, unsubstituted formamides, substitutedacetamides, and unsubstituted acetamides. Specific examples ofcosolvents that are preferably employed in the practice of thisinvention include, but are not limited to, 1,5-pentanediol,2-pyrrolidone, 2-ethyl-2-hydroxymethyl-1,3-propanediol, diethyleneglycol, 3-methoxybutanol, and 1,3-dimethyl-2-imidazolidinone. Cosolventscan be added to reduce the rate of evaporation of water in the ink-jetto minimize clogging or other properties of the ink such as viscosity,pH, surface tension, optical density, and print quality. The cosolventconcentration can range from about 1 wt % to about 40 wt %, and in oneembodiment is from about 2 wt % to about 30 wt %. Multiple cosolventscan also be used, as is known in the art.

Various buffering agents or pH adjusting agents can also be optionallyused in the ink-jet ink compositions of the present invention. Typicalbuffering agents include such pH control solutions as hydroxides ofalkali metals and amines, such as lithium hydroxide, sodium hydroxide,potassium hydroxide; citric acid; amines such as triethanolamine,diethanolamine, and dimethylethanolamine; hydrochloric acid; and otherbasic or acidic components which do not substantially interfere with thebleed control or optical density characteristics of the presentinvention. If used, buffering agents typically comprise less than about10 wt % of the ink-jet ink composition.

In another aspect of the present invention, various biocides can be usedto inhibit growth of undesirable microorganisms. Several non-limitingexamples of suitable biocides include benzoate salts, sorbate salts,commercial products such as NUOSEPT (Nudex, Inc., a division of HulsAmerica), UCARCIDE (Union Carbide), VANCIDE (RT Vanderbilt Co.), andPROXEL (ICI Americas) and other known biocides. Typically, such biocidescomprise less than about 5 wt % of the ink-jet ink composition and oftenfrom about 0.1 wt % to about 0.25 wt %.

In an additional aspect of the present invention, binders can beincluded in the liquid vehicle of the ink-jet ink which act to securethe colorants on the substrate. Binders suitable for use in the presentinvention typically have a molecular weight of from about 1000 Mw toabout 3,000,000 Mw. Non-limiting examples include polyester,polyester-melanine, styrene-acrylic acid copolymers, styrene-acrylicacid-alkyl acrylate copolymers, styrene-maleic acid copolymers,styrene-maleic acid-alkyl acrylate copolymers, styrene-methacrylic acidcopolymers, styrene-methacrylic acid-alkyl acrylate copolymers,styrene-maleic half ester copolymers, vinyl naphthalene-acrylic acidcopolymers, vinyl naphthalene-maleic acid copolymers, and salts thereof.

If surfactants are present, then typical water-soluble surfactants suchas TRITONS™ (including ethoxylated octylphenols), IGEPALS™ (includingalkyl phenoxypoly (ethleneoxy) ethanols), SILWETS™ (including siliconeglycol copolymers including polyalkylene oxide-modifiedpolydimethylsiloxanes, SURFYNOLS™ (including ethoxlyated tetramethyldecyndiols), TERGITOLS™ (including ethoxylated trimethylnonanols),BRIJS™ (including polyoxyethylene ethers), PLURONICS™ (includingethylene oxide/propylene oxide copolymers), FLUORADS™ and ZONYLS™(including fluorosurfactants), and NEODOLS™ (including nonionicethoxylated surfactants). Other surfactants or wetting agents that canbe used include Wetting Olin10G, alkyl polyethylene oxides, alkyl phenylpolyethylene oxides, polyethylene oxide (PEO) block copolymers,acetylenic PEO, PEO esters, PEO amines, PEO amides, and dimethiconecopolyols. Any of these surfactants, or combination of these surfactantsor other surfactants, can be present at from 0.01 wt % to about 10 wt %of the ink-jet ink composition.

EXAMPLES

The following examples illustrate the embodiments of the invention thatare presently best known. However, it is to be understood that thefollowing are only exemplary or illustrative of the application of theprinciples of the present invention. Numerous modifications andalternative compositions, methods, and systems may be devised by thoseskilled in the art without departing from the spirit and scope of thepresent invention. The appended claims are intended to cover suchmodifications and arrangements. Thus, while the present invention hasbeen described above with particularity, the following examples providefurther detail in connection with what are presently deemed to be themost practical and preferred embodiments of the invention.

Example 1 Dispersion of Fumed Silica in Water without ACH Treatment(Silica 1, 0% ACH, 0% Silane)

About 1.25 g of Li₂CO₃ and 400 g of deionized water were charged in a 1L stainless beaker. A high shear and high torque air mixer was used foringredient mixing and ingredient addition. About 100 g of Cab-O-Sil M-5(fumed silica from Cabot Corp. having a surface area of 200 m²/g) wasadded portion-wise, and 4M HCl was added concurrently to keep pH below4.0. The viscosity of the dispersion increased rapidly with the additionof silica, but reduced dramatically with the adjustment of pH. After theaddition of the fumed silica, the dispersion was further sheared with arotor/stator (Silverson L4RT-W) at 7000 RPM for 30 minutes. TheBrookfield viscosity was about 114 cps, and the solids content was 20 wt%.

Example 2 Dispersion of Fumed Silica in Water with ACH Treatment (Silica2, 10% ACH, 0% Silane)

About 1.25 g of Li₂CO₃, 27.4 g of Locron (50% of aluminumchlorohydrol inwater from Clariant Chemical Co.), and 346.4 g of deionized water weremixed and stirred with a high torque air mixer until all of thecomponents were dissolved. Next, about 125 g of Cabo-O-Sil M-5 (fumedsilica from Cabot Corp. having a surface area of 200 m²/g) were added tothe mixture portion-wise to prevent the silica from undesirablysolidifying. The total addition time was about 40 minutes. About 125 mlof deionized water was then added and the dispersion was further shearedwith a rotor/stator (Silverson L4RT-W) at 7000 RPM for 30 minutes. TheBrookfield viscosity was about 146 cps, the pH was 3.84, and the solidscontent was about 20 wt %.

Example 3 Aminosilane Reagent Modification of Silica without pHMonitoring (Silica 3, 0% ACH, 5% Silane)

About 30 g of the silica dispersion prepared in accordance with Example1 was reacted with 1.5 g of aminosilane reagent (20 wt % SilquestA-1120; aminoethylaminopropyl trimethoxysilane in ethanol) in a magneticstirrer. The initial pH of the silica dispersion was about 3.0, and theaminosilane reagent was added in five equal portions to the silicadispersion. The dispersion solidified undesirably almost immediatelywith the addition of aminosilane reagent.

Example 4 Aminosilane Reagent Modification of ACH Surface ActivatedSilica without pH Monitoring (Silica 4, 10% ACH, 5% Silane)

About 30 g of the surface activated silica dispersion prepared inaccordance with Example 2 was reacted with 1.5 g of aminosilane reagent(20 wt % Silquest A-1120; aminoethylaminopropyl trimethoxysilane inethanol) in a magnetic stirrer. The initial pH of the silica dispersionwas about 3.0, and the aminosilane reagent was added in five equalportions to the silica dispersion. The dispersion solidified undesirablyupon addition of the third portion of the aminosilane reagent.

Example 5 Aminosilane Reagent Modification of Silica (without ACH) withpH Monitoring (Silica 5, 0% ACH, 5% Silane)

About 30 g of the silica dispersion prepared in accordance with Example1 was reacted with 1.5 g of aminosilane reagent (20 wt % SilquestA-1120; aminoethylaminopropyl trimethoxysilane in ethanol) in a magneticstirrer by adding the aminosilane reagent dropwise. The pH wascontinuously monitored and adjusted with 1 M HCl to maintain the pH atfrom about 3 to 3.5. After about a quarter of the aminosilane reagentwas added, the pH of the dispersion increased very rapidly and thesilica dispersion solidified.

Example 6 Aminosilane Reagent Modification of ACH Surface ActivatedSilica with pH Monitoring (Silica 6, 10% ACH, 5% Silane)

About 30 g of the surface activated silica dispersion prepared inaccordance with Example 2 was reacted with 1.5 g of aminosilane reagent(20 wt % Silquest A-1120; aminoethylaminopropyl trimethoxysilane inethanol) in a magnetic stirrer by adding the aminosilane reagentdropwise. The pH was continuously monitored and adjusted with 1 M HCl tomaintain the pH at from about 3 to 3.5. After all of the aminosilanereagent was added, a stable, low viscosity treated silica dispersion wasobtained.

Example 7 Aminosilane Reagent Modification of ACH Surface ActivatedSilica with pH Monitoring (Silica 7, 10% ACH, 3% Silane)

About 30 g of the surface activated silica dispersion prepared inaccordance with Example 2 was reacted with 0.9 g of aminosilane reagent(20 wt % Silquest A-1120; aminoethylaminopropyl trimethoxysilane inethanol) in a magnetic stirrer by adding the aminosilane reagentdropwise. The pH was continuously monitored and adjusted with 1 M HCl tomaintain the pH at from about 3 to 3.5. After all of the aminosilanereagent was added, a stable low viscosity treated silica dispersion wasobtained.

Example 8 Dispersion of Fumed Silica in Water with ACH Treatment (Silica8, 5% ACH, 0% Silane)

About 0.625 g of Li₂CO₃, 13.7 g of Locron (50% of aluminumchlorohydrolin water from Clariant Chemical Co.), and 360.1 g of deionized waterwere mixed and stirred with a high torque air mixer until all of thecomponents were dissolved. Next, about 125 g of Cabo-O-Sil M-5 (fumedsilica from Cabot Corp. having a surface area of 200 m²/g) were added tothe mixture portion-wise to prevent the silica from undesirablysolidifying. The total addition time was about 40 minutes. About 125 mlof deionized water was then added and the dispersion was further shearedwith a rotor/stator (Silverson L4RT-W) at 7000 RPM for 30 minutes. TheBrookfield viscosity was about 40 cps, the pH was 3.5, and the solidscontent was about 20 wt %.

Example 9 Aminosilane Reagent Modification of ACH Surface ActivatedSilica with pH Monitoring (Silica 9, 5% ACH, 5% Silane)

About 30 g of the surface activated silica dispersion prepared inaccordance with Example 8 was reacted with 1.5 g of aminosilane reagent(20 wt % Silquest A-1120; aminoethylaminopropyl trimethoxysilane inethanol) in a magnetic stirrer by adding the aminosilane reagentdropwise. The pH was continuously monitored and adjusted with 1 M HCl tomaintain the pH at from about 3 to 3.5. After all of the aminosilanereagent was added, a stable low viscosity treated silica dispersion wasobtained.

Examples 1 to 9 demonstrate typical methods of dispersing fumed silicawith and without the presence of ACH, and treating the silica dispersionwith various levels of aminosilanes. ACH can also be added to the silicadispersion after the dispersion is finished. In general, the mixture canbe aged at elevated temperature for a certain time until theconductivity of the dispersion is reduced to a minimum. This sameprinciple can be used for the dispersion and treatment of differenttypes of fumed silica (surface area, aggregate size, etc.) and differentsilane coupling agents.

Example 10 Viscosity Stability Study

Four fumed silica coating compositions prepared above were used asink-jet coating recording materials. The formulations, based on dryparts by weight, are shown in Table 1 below, as follows:

TABLE 1 Ingredient Coating 1 Coating 2 Coating 3 Coating 4 Cab-O-Sil M-5100 parts (control) Silica 2 100 parts Silica 7 100 parts Silica 9 100parts Mowiol 25 parts 25 parts 25 parts 25 parts 2688(PVA) ¹Dyestabilizer 2.08 parts 2.08 parts 2.08 parts 2.08 parts Boric acid 3.57parts 3.57 parts 3.57 parts 3.57 parts Wetting agent 0.248 parts 0.248parts 0.248 parts 0.248 parts Glycerol 1.42 parts 1.42 parts 1.42 parts1.42 parts ²% Solid 18 18 18 18 ¹Optional ingredient to interact withdye upon printing to improve print quality ²Water was added in an amountto provide the percentage of solids indicated.

Example 11 Viscosities of Coating Compositions

The viscosities of the coatings prepared in accordance with Example 10were tested, as shown in Table 2 below:

TABLE 2 0 minutes 60 minutes 120 minutes 180 minutes Coating 1 >10,000cps     — — — (M-5 control) Coating 2 1240 cps 2640 cps 3010 cps 3492cps (Silica 2) Coating 3 1120 cps 1236 cps 1452 cps 1788 cps (Silica 7)Coating 4  430 cps  360 cps  486 cps  500 cps (Silica 9)

The viscosity of Coatings 1 to 4 was measured by Brookfield Viscometer(Model VR-7714) at 40° C. Based on the viscosity measurements, the fumedsilica dual treated with ACH and aminosilane reagent not only reducedfluid viscosity, but also greatly improved the long term stability ofthe coating fluid. Table 2 depicts the relative stability of Coatings 3and 4. Though still an improvement over untreated silica, Coating 2became generally more viscous over time, i.e. more solidified or gelledover time. Coating 1 (unmodified Cab-O-Sil M-5) had extremely highviscosity and could not be stirred.

Example 12 Image Quality and Humid Fastness of Ink-Jet RecordingMaterials Including ACH-Modified and/or Aminosilane-Modified Silica

Cab-O-Sil LM-130 from Cabot Chemicals was treated with differentcombinations of ACH and aminoalkylsilsesquioxane oligomer (tradenameWSA-9911 by Gelest Inc.). The detailed formulations are shown in Table 3below. These modified silica compositions were used to prepare porousink-jet recording coatings based on the formulation described in Table4.

TABLE 3 Silica 10 Silica 11 Silica 12 Silica 13 Silica 14 ³LM-130LM-130* LM-130 LM-130 LM-130 LM-130 ACH 0 wt % 1.5 wt % 3.5 wt % 5.25 wt% 7.0 wt % ⁴Amino- 4 wt %   3 wt %   2 wt %   1 wt %   0 wt % silane³Cab-O-Sil LM-130 (Cabot Corp.). ⁴22-25% solid aminoalkylsilsesquioxaneoligomer in water (Gelest Inc.)

TABLE 4 Ingredient Amount (dry) Silica 10, 11, 12, 13, or 14 73.84 wt %Mowiol (PVA) 18.48 wt % Dye stabilizer  3.02 wt % Boric acid  3.10 wt %Nonionic surfactant  0.91 wt % Glycerol  0.65 wt %

The aminosilane reagent treated silica (Silica 10), provided poorcoalescence, but showed some air fade resistance gain. Aluminum chloridehydrate (ACH) treated silica (Silica 14), provided good coalescenceperformance, but exhibited poor air fade resistance. By incorporatingboth ACH and the aminosilane reagent (Silicas 11-13), a balance betweenthe good air fade resistance and good coalescence was achieved.

While the invention has been described with reference to certainpreferred embodiments, those skilled in the art will appreciate thatvarious modifications, changes, omissions, and substitutions can be madewithout departing from the spirit of the invention. It is thereforeintended that the invention be limited only by the scope of the appendedclaims.

1. A media sheet having a treated silica particulate-containing coating,comprising: a) a porous coating composition, including: i) treatedsilica particulates being surface-activated by a surface activatingagent selected from the group consisting of an aluminum chloridehydrate, a trivalent metal oxide, a tetravalent metal oxide, andcombinations thereof, said treated silica particulates also beingreagent-modified by an organosilane reagent, and ii) a binder admixedwith the treated silica particulates; and b) a media substrate havingthe porous coating composition coated thereon.
 2. A media sheet as inclaim 1, wherein the silica particulates are from 10 nm to 500 nm insize.
 3. A media sheet as in claim 1, wherein the organosilane reagentis an amine-containing silane.
 4. A media sheet as in claim 3, whereinthe amine-containing silane includes a quaternary ammonium salt.
 5. Amedia sheet as in claim 1, wherein the media substrate is photobase orpaper.
 6. A media sheet as in claim 1, wherein the silica particulatesare surface-activated and reagent-modified in an aqueous environment. 7.A media sheet as in claim 1, wherein the surface activating agent isaluminum chloride hydrate.
 8. A system for printing ink-jet images withminimal dye mobility, comprising: a) a media sheet having a porouscoating composition, including: i) treated silica particulates beingreagent-modified and surface-activated in an aqueous environment,wherein the treated silica particulates have a net positive charge, ii)a binder admixed with the treated silica particulates to form the porouscoating composition, and iii) a media substrate having the porouscoating composition coated thereon; and b) an ink-jet ink having ananionic dye colorant configured for being printed on the media sheet. 9.A system as in claim 8, wherein the treated silica particulates aresurface activated by a member selected from the group consisting of analuminum chloride hydrate, a trivalent metal oxide, a tetravalent metaloxide, and combinations thereof, and wherein the treated silicaparticulates are reagent-modified by aluminum chloride hydrate.